Reaction product of unsaturated mono-glycol ethers and unsaturated nitriles



Patented July 9, 1946 MONO-GLYCOL ETHERS RATED NITRILES AND U NS A'ITU ih I p Edward John S chwoegler, Wya'ndotte,Mich., as- I f;- slgnor toWyandotte Chemicals Corporation,

' No Drawing.

The present invention relates to chemical com-' pounds of the followingindicated general formula, and their method of preparation:

R= unsaturated hydrocarbon radical R =a hydrogen or alkyl group 7 1A1;example of such product is the following;

.. g w lweemm me,

Briefly outlined, my invention involves the reaction of a "monoglycolether of; an unsaturated alcohol, with an czfi unsaturated open chainnitrile, inthepresence of an alkaline condensing agent. 'Such' openchain nltrile possesses the a ar 1; a

capo-GEN where 1i. hydrogen or a methyl group, vizz acrylonitrileor amethyl aorylonitrilet I hol are suitably prepared by the reaction ofolefin oxides and the unsaturated. alcohol, such as illustrated by thefollowing chemical equatiom- Wyandotte, Mich., a corporation of MichiganApplication November 22, 1944, v v 7 Serial No. 564,716 "31:1 .7. I v V14 Claims. (01. 26034;5)

' carbon atom of the nitrile becomes linked to" the oxygen of suchhydroxyl group, substantially as illustrated by the following equation:

, a v. Suzanne CHz=GHCH1O CHICHIOH CHFCHCEN h catalyst may be employedinthe performance of my presom=onomoomomon Such ethers may alternativelybe prepared by reaction of the alkali metal salt of the unsaturatedalcohol and an olefin chlorhydrin, thusly:

#:The mono-glycol ethers of an unsaturatedalco- Anyl alcoholentinventioni ethylene, propylene and butylene "glycol ethers of thefollowing listed unsaturated alcoholsf A Oleyl alcohol Propargyl alcoholCinnamyl alcohol Methylallyl alcohol Furfuryl alcohol Crotyl alcoholGeraniol Methylvinylcarbinol Linalool Allylcarbinol CitronellolPentene-1-ol-5 Alpha terpineol of ethers is within the purview and scopeof my present invention.

The process is carried out in general by slowly adding acryloormethacrylonitrile to the ether containing the catalyst; the rate ofaddition being 7 regulated so that the temperature of the reactionmixture-remains below 70 C. External cooling may be employe'd'ifdesired. The reactants may beemployed in 'equimolar proportions althoughit is sometimes advantageous to use a small excess of unsaturated ether.

By way of further'explanation and illustration of my invention, in orderthat it may readilybe 3 understood and practiced by those skilled in theart, the following examples are given:

Example 1 Mono allyl ether of ethylene glycol in the amount of 671 gramswas placed in a reaction vessel fitted with an agitator and surroundedby a jacket suitable for heating or cooling. Methyl alcohol (10 grams)were added to the ether followed by the addition of grams ofv sodium insmall chips. The mixture was agitated until all sodium had dissolved.Acrylonitrile (265 grams) were added to the agitated mixture over aperiod of 2 hours while the reactants mixture was maintained at atemperature of 18-20" C. The reaction mixture was agitated for 1 hour atthe above temperature on completion of acrylonitrile addition and thenpoured into 200 cc. of water and neutralized with dilute sulfuric acid.The oily layer was separated from the aqueous layer, washed two timeswith sodium chloride solution, dried and distilled. A water whiteproduct boiling at 110 C. at 2 mm. Hg pressure (and weighing 620 grams)was obtained. with the formula:

CI-Iz='CHCH2O-CI-lz" CH2,OCH2CH2-CEN B(allyloxy ethoxy) propionitrileExample 2 Mixed mono allyl ether of propylene glycol (232 grams) wereplaced in a reaction vessel fitted with an agitator, dropping device anda reflux condenser. Two grams of sodium were added to the ether in smallchips and the mixture warmed to-80 C. to effect solution. The solutionwas cooled to 15 C. by means of an ice bath. Acrylo-- nitri'le (98'grams) was added to the agitated glycol ethers containing the dissolvedsodium over a'period of 3 hours. The temperature of the reaction masswas maintained between 15 and 25 C; during theaddition period. After allacrylonitrile had been added, the reaction mass was agitated for 30minutes at 20 C., poured into water and neutralized with hydrochloricacid. The aqueous, layer was separated from the oily condensationproduct. The crude condensation product was then distilled under vacuum.Two hundred and forty-five grams of the desired condensation productsboiling at 138 to 142 C. at 12 mm. Hg pressure were obtained. Analysisshowed they products. to be ,B-cyano ethyl ethers of mono allylpropylene glycol ethers.

Example 3 One hundred and sixteen grams of 1,-allyloxypropanol-2,prepared by the interaction of sodium allylate and l-chloro-propanol-Z,were condensed with 49 grams of acrylonitrile, 1 gram of sodium beingused as a catalyst, by the same procedure as set out in Example 2. Onehundred and twenty grams of l-allyloxy 2(B-cyanoethoxy) propane boilingat 140 to 142C. at 12 mm. Hg pressure were obtained.

' Escample 4 Metallic-sodium (1 gram) in the form of thin chips wasdissolved in 108 grams of the furfuryl ether of ethylene glycol byvigorously agitating the mixture at 25 to 28 C. Acrylonitrile (38 grams)Was added to the agitated ether over a period of 2 hours while thetemperature was maintained below 25 C. by meansof an external coolingbath. The reaction mixture was then stirred for ,5 hour at 25 C. andpoured into water containing just sufficient H2804 to neutralize the Itsanalysis agreed dissolved sodium. The oily reaction mass was separatedfrom the aqueous layer, washed with water, dried and distilled.Fifty-four grams of Mfurfuroxy ethoxy) propionitrile boiling at 152 to154 C. at 1 mm. Hg pressure were obtained. Nitrogen analysis showed thiscompound to be ractically pure.

I claim:

1. As anew composition of matter, thereaction product of an ether of asaturated glycol and an unsaturated alcohol, and an an unsaturated openchain nitrile,

2. As a new composition of matter, the reaction product of an ether of asaturated glycol and an unsaturated alcohol, and acrylonitrile.

3. As a new composition of matter, ,8- (allyloxy ethoxy)propionitrile-.-

4. As a new composition of matter, a mixture of [i cyano ethyl ethers ofmono allyl propylene glycol ethers.

5. As a new composition of matter, l-allyloxy -2 [i cyanoethoxy propane.

6. As a new composition of matter, 18(furfuroxy ethoxy) propionitrile,

'7. The method of making chemical compounds of the formula where R is anunsaturated hydrocarbon radical, and Y is an alkylene group, consistingin reacting an ether of asaturated glycol and an unsaturated alcoholwith an unsaturated open chain nitrile in the presence of an alkalinecondensing agent. n

8. The method of making chemical compounds of the formula where R is anunsaturated hydrocarbon radical,

and Y is an alkylene group, consisting in reacting an olefin oxide andan unsaturated alcohol, to form an unsaturated mono-glycol ether-andthen reacting the latter with an open chain nitrile in the presence ofan alkaline condensing agent.

9. The method of making chemical compounds of the formula W of theformula Where R is an unsaturated hydrocarbonradical, and Y is analkylene group consisting in reacting the sodium salt of an unsaturatedalcohol with a mixture of ethylene and propylene chlorhydrins to formmixed unsaturated mono-glycol ethers and then reacting the. latter withan open chain nitrile. in. the presence ofv analkaline condensing agent,

11. The method oimaking aichemical.v compound ofclaim 3 consisting inreacting, mono allyl ether of ethylene glycol with acrylonitrile in. thepresence of dissolved metallic sodium. at a temperature of 18 to 20 C.,neutralizing thereaction mixture and then separating and distilling thedesired product therefrom.v 1

12. The method of making a chemical compound of claim 4 consisting ofreacting a mixture of mono allyl ethers of mono propylene glycol withacrylonitrile in the presence of dissolved metallic sodium at atemperature of 15 to 25 C., neutralizing the reaction mixture,separating and distilling the desired product. r

13. The method of making a product of claim 5 consisting in reactingsodium allylate and 1- chloro-propanol-Z to form l-allyloxy propionol-2,condensing the product thereof with acrylonitrile in the presence ofdissolved metallic sodium at a temperature of 15 to 25 0., neutralizingthe resultant mixture andthen separating and distilling the desiredproduct.

14. The method of making the product or claim 6 consisting in reactingfurfuryl ether of ethylene lycol with acrylonitrile in the presence ordissolved metallic sodium at a temperature below 25 0., neutralizing theresultant mixture and then separating and distilling the desiredproduct.

EDWARD JOHN SCHWOEGLER.

